2-Optionally substituted alkyl-and phenylsulfonylphenyl-azo-phenyl dyes and a process for their synthesis

ABSTRACT

Compounds of the formula ##STR1## wherein R 1  is optionally substituted hydrocarbyl (alkyl or phenyl), 
     R 2  is hydrogen, alkyl or acylamino, 
     R 3  is hydrogen, alkyl, substituted alkyl, alkoxy or substituted alkoxy, 
     Each of R 4  and R 5  is independently hydrogen, alkyl or substituted alkyl, 
     T is halo, nitro, cyano, alkyl, alkoxy, alkylsulfonyl, sulfamoyl or alkylsulfamoyl, and 
     n is 0 to 3. These compounds are suitable for the dyeing and printing of textile materials. The dyeings obtained are extremely fast to thermofixation, sublimation, pleating, gas fumes, cross dyeing, rubbing, dry cleaning, chlorine, and wet treatments, such as water, washing and perspiration. The compounds of this invention and other phenylazo-phenyl compounds with an optionally substituted hydrocarbylsulfonyl group (R 1--  SO 2  --) on the diazo component radical in a position ortho to the azo group can be synthesized from the corresponding compounds having a halo atom or nitro group in this position by reaction with a compound of the formula H--SO 2  --R 1  or a salt thereof.

It has been found that azo compounds of the formula ##STR2## in which R₁stands for a hydrocarbon radical which may be substituted and/or maycontain hetero atoms,

R₂ for a hydrogen atom, an alkyl group or acylamino group which may besubstituted,

R₃ for a hydrogen atom or an alkyl or alkoxy group which may besubstituted,

R₄ for a hydrogen atom or an alkyl group which may be substituted and

R₅ for a hydrogen atom or an alkyl group which may be substituted byhalogen atoms or by cyano alkoxy, phenyl, phenoxy, pyridyl, acyl,acyloxy, amino, alkylamino, or acylamino groups which may bear furthersubstituents,

And where the nucleus A may bear further substituents, can be obtainedby condensing 1 mole of an azo compound of the formula ##STR3## where Zrepresents a halogen atom or a nitro group, with 1 mole of a sulphinateof the formula

    H--SO.sub.2 --R.sub.1                                      (III)

or of a salt thereof.

Examples of suitable substituents on the alkyl or alkoxy groups, whichcontain preferably 1, 2, 3 or 4 carbon atoms, are halogen atoms, bywhich (in particular) chlorine or bromine atoms are understood, cyano,thiocyano, hydroxyl, mercapto, amino, alkoxy (with 1 to 4 carbon atoms),phenyl, phenoxy, acyl, acyloxy and acylamino groups. The nuclei ofaromatic character may bear, besides the aforenamed substituents, e.g.nitro and alkyl groups, the latter preferably with 1 to 4 carbon atoms.

Groups of the formulae R--X-- and R'--Y-- are examples of suitable acylradicals; in these formulae

R stands for a hydrocarbon radical which may contain hetero atoms and/orbear further substituents, preferably an alkyl or phenyl radical whichmay be substituted as described above,

X for a group of the formula --O-- CO-- or --SO₂ --,

R' for a hydrogen atom or R,

Y for a group of the formula --CO--, --NR"CO-- or --NR"SO₂ -- and

R" for a hydrogen or R.

The preferred compounds of formula (I) are of the formula ##STR4## whereR₁₁ stands for a lower alkyl radical which may bear a chlorine orbromine atom; a phenyl radical which may bear as substituents fluorine,chlorine, bromine or iodine atoms, hydroxyl, methyl, amino, methylamino,nitro or acetylamino groups; or a pyridyl radical;

R₁₂ for a hydrogen atom or a lower alkyl radical; a formylamino radical;a lower alkylcarbonylamino radical which may be substituted by chlorineor bromine atoms, acetoxy, methoxy, ethoxy or phenoxy groups; amethoxycarbonylamino, ethoxycarbonylamino, benzoylamino, (benzamido)methylsulphonylamino or ethylsulphonylamino radical;

R₁₃ for a hydrogen atom or a lower alkyl or alkoxy radical;

R₁₄ for a hydrogen atom or an alkyl group with 1 to 4 carbon atoms whichmay bear as substituents a cyano, hydroxyl, methoxy, ethoxy,cyanoethoxy, formyloxy, acetoxy, propionyloxy, methoxycarbonyl,ethoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy, acetoxyethoxy orphenyl group;

R₁₅ for a hydrogen atom or an alkyl group with 1 to 4 carbon atoms whichmay bear as substituents a hydroxyl, methoxy, ethoxy, cyanoethoxy,phenoxy, phenyl, pyridyl methylpyridyl, pyridylethoxy, methylamino,ethylamino, formyloxy, acetoxy, propionyloxy, benzoyloxy,methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, methoxycarbonyloxy,ethoxycarbonyloxy, phenoxycarbonyloxy, methoxyethoxycarbonyl,phthalimide, sulphophthalimide or succinimide group, or a cationic groupof one of the formulae --N⁺ (CH₃)₂ --NH₂, --N⁺ (CH₃)₃, --N⁺ (C₂ H₅)₃,##STR5## and where the nucleus B may bear as further substituentschlorine or bromine atoms, cyano, nitro, methyl, methoxy,methylsulphonyl, ethylsulphonyl, aminosulfonyl (sulfamoyl) ormethylaminosulfonyl (methylsulfamoyl) groups.

Representative compounds of Formula I are those of the formulae ##STR6##wherein R₁, R₂, R₃, R₄ and R₅ are as defined above, and

Ring D may bear further substituents, and particularly those of theformulae ##STR7## wherein R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are as definedabove, and

Ring E may bear fluoro, chloro, bromo, iodo, hydroxy, methyl, amino,methylamino, nitro or acetamido substituents.

Alkyl and alkoxy groups denoted as "lower" bear 1 to 4 or preferably 1or 2 carbon atoms.

The compounds of formula (IV) are obtained by condensing 1 mole of anazo compound of the formula ##STR8## where Z₁ represents a chlorine,bromine or iodine atom or a nitro group,

with 1 mole of a compound of the formula

    H--SO.sub.2 --R.sub.1                                      (VI)

or a salt thereof.

The preferred salts of compounds of formulae (III) and (VI) are those ofalkaline metals and alkaline-earth metals, in particular the sodium,potassium, magnesium and calcium salts.

The reaction is effected preferably in an organic sovlent, although anaqueous suspension can be used. Examples of suitable solvents are:

a. alcohols, ethers and esters, in particular amyl alcohol, glycolmonomethylether, glycol monoethylether, diethylene glycolmonomethylether and glycol monoethyletheracetate;

b. carboxylic acid amides, N-substituted carboxylic amides,dialkylsulphoxides and dialkylsulphones, e.g. formamide,dimethylformamide, dimethylsulphoxide, dimethylacetamide,N-methylpyrrolidone and tetramethylenesulphone;

c. other nitrogenous solvents, such as quinoline, acetonitrile,benzonitrile and phosphoric acid-tris-dimethylamide.

The halogen atoms are easier to exchange than nitro groups, so azocompounds whose diazo components are bound to a nitro group in oneortho-position to the azo group and to a halogen atom in the otherortho-position can be reacted without difficulty so as to retain thenitro group. By employing the azo compound in slight excess relativelyto the compound of formula (III) or (VI), ortho-ortho'-dihalogeno-azocompounds can be readily reacted so that only one halogen atom isexchanged.

The new process according to the present invention makes possible theproduction of compounds which hitherto have not been known. For example,the compounds of Formulae VII, VIII, IX and X.

It is desirable to convert the new dyes thus obtained into dyepreparations before application, when they are sparingly soluble inwater. They are worked up as dye preparations in the normal way, e.g. bygrinding in the presence of dispersion agents and/or fillers, withsubsequent drying in a vacuum or atomizer drier if dry preparations arerequired. Upon addition of a suitable volume of water, the dyepreparations can be utilized for exhaust dyeing, pad dyeing and printingfrom long or short baths.

From aqueous dispersion the dyes build up well on textiles made ofsynthetic or semi-synthetic hydrophobic organic substances of highmolecular weight. They are particularly suitable for the dyeing andprinting of textiles of polyester, cellulose acetate, cellulosetriacetate and polyamide fibres. They are also dyeable on polyolefins.

Those dyes which contain a nitrogen atom capable of salt formation arehighly suitable, especially in the form of their salts, for dyeingpolyacrylonitrile fibres.

Known exhaustion dyeing, padding and printing processes are employed,for example the one described in French Pat. No. 1,445,371.

The dyeings obtained are extremely fast to thermofixation, sublimation,pleating, gas fumes, cross dyeing, rubbing, dry cleaning, chlorine, andwet treatments, such as water, washing and perspiration. They are highlystable to the action of the pre-cure and post-cure permanent pressfinishing processes. The dischargeability and reserve of wool and cottonare good. The light fastness is excellent, even in pale shades, so thenew dyes are very suitable as components for the production offashionable pastel shades.

In the following Examples the parts and percentages are by weight andthe temperatures in degrees centigrade.

EXAMPLE 1

18 Parts of a 30% aqueous solution of sodium methanesulphinate (H₃C--SO₂ --Na) are added to a solution of 23 parts of2-bromo-4-nitro-6-cyano-2'-acetylamino-4'-diethylamino-1,1'-azobenzenein 300 parts of dimethylformamide at 20°-25°. The solution is raised to60°-65° and stirred to 6 hours, then it is cooled to 25° and dilutedwith 500 parts of methanol. The dye settles out and is filtered off,washed with methanol and dried. It dyes synthetic fibres in blue shadeswith excellent fastness properties. In place of2-bromo-4-nitro-6-cyano-2'-acetylamino-4'-diethylamino-1,1'-azobenzene,the equimolecular amount of 2-chloro - or2-iodo-4-nitro-6-cyano-2'-acetylamino-4'-diethylamino-1,1'-azobenzene or2,4-dinitro-6-cyano-2'-acetylamino-4'-diethylamino-1,1'-azobenzene and,in place of sodium methanesulphinate can be employed potassium, calciumor magnesium methanesulfinate, with equally good results.

EXAMPLE 2

A solution of 26.7 parts of sodium benzenesulphinate (H₅ C₆ --SO₂ --Na)are added to a solution of 23 parts of2-bromo-4-nitro-6-cyano-2'-methoxycarbonylamino-4'-N,N-diethylamino-1,1'-azobenzenein 450 parts of dimethylformamide at 60°-65°. The reaction solution isstirred for 8 hours at 60°-65° and for 2 hours at 75°-80°. It is thencooled to 0° and, after stirring for 20 minutes at this temperature, theprecipitated dye is filtered off. The filter residue is washed, firstwith methanol and then with water, and subsequently dried. On syntheticfibres the dye thus obtained gives dyeings of blue shade with excellentfastness properties.

EXAMPLE 3

A solution of 29 parts of sodium benzenesulphinate, 70 parts ofdimethylformamide and 30 parts of water is added to a solution of 57.5parts of2-bromo-4-nitro-6-cyano-2'-acetylamino-4'-N,N-di-β-acetoxyethylamino-1,1'-azobenzenein 350 parts of dimethylformamide at 60°-65°. The reaction solution isstirred for 8 hours at 60°-65° and then for 2 hours at 70°. On coolingto 0°, the precipitated dye is filtered off, washed with petroleum etherand then with water, and dried. The dye thus obtained dyes syntheticfibres in blue shades with excellent fastness properties.

The dyes listed in the following Table 1 correspond to the formula##STR9## and can be produced in accordance with the procedures given inExamples 1 to 3.

    Table 1      Example      Shade on Pol-  No R.sub.1 R.sub.2 R.sub.4 R.sub.5 R.sub.3     ester fibre      4 CH.sub.3 NHCHO CH.sub.2CH.sub.2OCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.sub.3      H blue   5 " " CH.sub.2CH.sub.2COOCH.sub.3 CH.sub.2CH.sub.2COOCH.sub.3     " "  6 " NHCOC.sub.2 H.sub.5 " " " "  7 " NHCOCH.sub.3 " " " "  8 " " "     " OC.sub.2 H.sub.5 "  9 " NHCOC.sub.2 H.sub.5 " " " " 10 " NHCHO " " " "     11 " NHCOCH.sub.3 " " H " 12 " NHCOC.sub.2 H.sub.5 " " H " 13 C.sub. 6     H.sub.5 NHCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.su     b.3 H " 14 " NHCHO " " H " 15 " CH.sub.3 " " H " 16 " " CH.sub.2CH.sub.2C     OOCH.sub.3 CH.sub.2CH.sub.2COOCH.sub.3 H " 17 " " CH.sub.2CH.sub.2CN     CH.sub.2CH.sub.2OCOCH.sub.3 H " 18 " " CH.sub.2CH.sub.3 " H " 19 " "     CH.sub.2CH.sub.2OCOCH.sub.3 " OC.sub.2 H.sub.5 " 20 C.sub.2 H.sub.5     NHCOCH.sub.3 CH.sub.2CH.sub.2CH.sub.2OCOCH.sub.3 CH.sub.2CH.sub.2CH.sub.2O     COCH.sub.3 " " 21      ##STR10##      NHCOCH.sub.3 CH.sub.2CH.sub.2OCH.sub.3 CH.sub.2CH.sub.2OCH.sub.3 " " 22      H "  CH.sub.2CH.sub.3 H red violet 23      ##STR11##      NHCOCH.sub.3 CH.sub.2CH.sub.2CN CH.sub.2CH.sub.2C.sub.6 H.sub.5 H blue     24 CH.sub.3 CH.sub.3 CH.sub.2CH.sub.3 CH.sub.2CHOHCH.sub.2OH H " 25     CH.sub.2Cl NHCOCH.sub.3 "      ##STR12##      OCH.sub.3 " 26 CH.sub.2CH.sub.2      Cl " "     ##STR13##      OC.sub.2 H.sub.5 " 27 CH.sub.3 NHCOC.sub.2 H.sub.5 CH.sub.2CH.sub.2CN      ##STR14##      H " 28 " NHCOCH.sub.3 "      ##STR15##      OCH.sub.3 " 29 " H CH.sub.2CH.sub.3      ##STR16##      H red violet 30 30 " NHCOCH.sub.3 "      ##STR17##      H blue 31 " " "      ##STR18##      H " 32 " H " CH.sub.2CH.sub.2OCOC.sub.6 H.sub.5 H red violet 33 " H "     CH.sub.2CH.sub.2COOC.sub.6      H.sub.5 H " 34     ##STR19##      NHCOCH.sub.3 CH.sub.2CH.sub.2CN CH.sub.2CH.sub.2OCOCH.sub.3 OCH.sub.3     blue 35 CH.sub.3 NHCHO " " " " 36      ##STR20##      CH.sub.3 " " H " 37 CH.sub. 3 H " CH.sub.2CH.sub.2OH H red violet 38 "     H " CH.sub.2CH.sub.2OCOCH.sub.3 H " 39      ##STR21##      " CH.sub.2CH.sub.3 H " 40 " H " H H " 41      ##STR22##      H CH.sub.2CH.sub.3 CH.sub.2CH.sub.3 H " 42 C.sub.6 H.sub.5 NHCOCH.sub.3     " " H blue 43 CH.sub.3 NHCOC.sub.2      H.sub.5 " " H " 44     ##STR23##      CH.sub.3 CH.sub.2CH.sub.2CN " H violet 45 " " " CH.sub.2CH.sub.2OH H "     46 CH.sub.3 NHCOOCH.sub.2CH.sub.3 CH.sub.2CH.sub.2OCOCH.sub.3 CH.sub.2CH.     sub.2OCOCH.sub.3 OC.sub.2      H.sub.5 blue 47 " NHCOCH.sub.2OCH.sub.2CH.sub.3 " " OCH.sub.3 " 48 "     NHCOC.sub.6 H.sub.5 " " OC.sub.2 H.sub.5 " 49 " NHCOCH.sub.2 C.sub.6     H.sub.5 " " " " 50 " NHCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.sub.3 " OCH.sub.3      " 51      ##STR24##      NHCOC.sub.2 H.sub.5 " " " " 52 CH.sub.3 NHCOCH.sub.3 CH.sub.2 CH.sub.2     OCH.sub.2 CH.sub.2 CN CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CN " " 53 "     NHCOCH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2      OCOCH.sub.3 CH.sub.2CH.sub.3 OC.sub.2 H.sub.5 " 54 " NHCOC.sub.6     H.sub.5 CH.sub.2CH.sub.2OCOOCH.sub.3 CH.sub.2CH.sub.2OCOOCH.sub.3     OCH.sub.3 " 55 " NHCOCH.sub.3 CH.sub.3 CH.sub.2CH.sub.2OH  C.sub.2     H.sub.5 " 56 " H C.sub.2 H.sub.5 CH.sub.2CH.sub.2OCOOC.sub.6 H.sub.5 H     red 57 " NHCOCH.sub.3 " CH.sub.2CH.sub.2OCOC.sub.6 H.sub.5 OCH.sub.3     blue 58 " " " CH.sub.2CH.sub.2OCOOC.sub.6 H.sub.5 OC.sub.2 H.sub.5 " 59     " " CH.sub.2CH.sub.2OCHO CH.sub.2CH.sub.2OCHO H " 60      ##STR25##      " " " OCH.sub.3 " 61 " " C.sub.4 H.sub.9 CH.sub.2CH.sub.2OCOCH.sub.3 "     " 62CH.sub.3 " " CH.sub.2CH.sub.2OH OC.sub.2      H.sub.5 " 63 " " " CH.sub.2CH.sub.2CN OCH.sub.3 " 64 " NHCOCH.sub.2 OH     CH.sub.3 CH.sub.3 " " 65 " NHCOCH.sub.2OCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.     sub.3 CH.sub.2CH.sub.2OCOCH.sub.3 OC.sub.2 H.sub.5 " 66" NHSO.sub.2     CH.sub.3 " " OCH.sub.3 " 67      ##STR26##      NHCOCH.sub.3 C.sub.2 H.sub.5 C.sub.2      H.sub.5 H " 68 CH.sub.3 " CH.sub.2CH.sub.2COOC.sub.2      H.sub.5 CH.sub.2CH.sub.2COOC.sub.2      H.sub.5 OCH.sub.3 " 69 " H CH.sub.2CH.sub.3      ##STR27##      H red violet 70 " CH.sub.3 C.sub.4      H.sub.9     ##STR28##      H violet 71 " H C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.2     OCH.sub.3 H red violet 72      ##STR29##      NHCOCH.sub.3 CH.sub.2CH.sub.2COOC.sub.2      H.sub.5 CH.sub.2CH.sub.2OCOOC.sub.2 H.sub.5 H blue 73 CH.sub.3 "     C.sub.2      H.sub.5     ##STR30##      OC.sub.2 H.sub.5 " 74 " " CH.sub.3 C.sub.6 H.sub.5 H " 75 " " C.sub.2     H.sub.5 C.sub.2 H.sub.4C.sub.6      H.sub.5 H " 76 " " CH.sub.2CH.sub.2OCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.sub     .3 CH.sub.3 " 77 C.sub.6 H.sub.5 NHCOC.sub.2 H.sub.5 C.sub.2 H.sub.5     C.sub.2      H.sub.5 H " 78     ##STR31##      " " " H " 79 CH.sub.3 NHCOOCH.sub.3 " " H " 80 C.sub.6 H.sub.5 " " " H     " 81      ##STR32##      NHCOOC.sub.2 H.sub.5 " " H " 82 CH.sub.3 " " " H " 83 C.sub.6 H.sub.5 "     " " H " 84      ##STR33##      NHCOOCH.sub.3 " " H " 85 CH.sub.3 NHCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.sub     .3 CH.sub.2CH.sub.2OCOCH.sub.3 H " 86 " NHCOC.sub.2 H.sub.5 " " H " 87     C.sub.6      H.sub.5 " " " H " 88     ##STR34##      " " " H " 89 CH.sub.3 NHCOOCH.sub.3 " " H " 90 C.sub.6 H.sub.5 " " " H     " 91      ##STR35##      " " " H " 92 " NHCOCH.sub.3 CH.sub.2CH.sub.2OCOC.sub.2      H.sub.5 CH.sub.2CH.sub.2OCOC.sub.2 H.sub.5 H " 93 CH.sub.3 " " " H " 94      ##STR36##      NHCOC.sub.2 H.sub.5 " "  H " 95 CH.sub.3 " " " H " 96 " NHCOOC.sub.2     H.sub.5 CH.sub.2CH.sub.2OCOCH.sub.3 CH.sub.2CH.sub.2OCOCH.sub.3 H " 97      ##STR37##      " " " H " 98 CH.sub.3 H C.sub.2 H.sub.5 CH.sub.2CH.sub.2OC.sub.6     H.sub.5 H red violet 99 C.sub.6 H.sub.5 NHCOCH.sub.3 " " H blue 100      ##STR38##      " " " H " 101       CH.sub.3 " CH.sub.2CH.sub.2OCH.sub.3 CH.sub.2CH.sub.2OCH.sub.3 H " 102      ##STR39##      " " " H " 103       CH.sub.3 " CH.sub.2CH.sub.2CN CH.sub.2CH.sub.2OCOCH.sub.3 H " 104     C.sub.6 H.sub.5 " " " H " 105      ##STR40##      " " " H " 106  " NHCOC.sub.2 H.sub.5 " " H " 107  C.sub.6 H.sub.5     NHCOCH.sub.2 OCH.sub.3 C.sub.2 H.sub.5 H " 108      ##STR41##      NHSO.sub.2 CH.sub.3 " " H " 109  CH.sub.3 NHCOCH.sub.2 OC.sub.6 H.sub.5     " " H " 110  C.sub.6 H.sub.5 NHCOCH.sub.2 CH.sub.2 OCH.sub.3 " " H " 111      " NHCOCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 " " H " 112      ##STR42##      NHSO.sub.2 C.sub.2 H.sub.5 " " H " 113  C.sub.6 H.sub.5  C.sub.2     H.sub.5 " " H violet 114  " NHCOCH.sub.3 CH.sub.2CH.sub.2CN C.sub.3     H.sub.7 H " 115      ##STR43##      " " CH.sub.2C.sub.6 H.sub.5 H " 116  " " C.sub.2      H.sub.5 CH.sub.2CH.sub.2OCOC.sub.2 H.sub.5 H " 117  " NHCOC.sub.2     H.sub.5 CH.sub.2CH.sub.2OCOC.sub.2 H.sub.5 CH.sub.2CH.sub.2OCOC.sub.2     H.sub.5 H " 118  C.sub.6      H.sub.5 NHCOCH.sub.3 H CH.sub.2CH.sub.2COCH.sub.3 H blue 119  " " "     CH.sub.2CH.sub.2COC.sub.2 H.sub.5 H " 120      ##STR44##      " C.sub.2 H.sub.5 CH.sub.2CH.sub.2OCH.sub.2CH.sub.2CN H " 121  " " "     CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCOC.sub.6 H.sub.5 H " 122     CH.sub.2 Br " " C.sub.2 H.sub.5 H " 123  CH.sub.2 CH.sub.2      OH " CH.sub.2CH.sub.2OCOCH.sub. 3 CH.sub.2CH.sub.2OCOCH.sub.3 H " 124      ##STR45##      " " " H " 125      ##STR46##      " " " H " 126      ##STR47##      NHCOOCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H " 127      ##STR48##      " " " H " 128      ##STR49##      " " " H " 129      ##STR50##      " " " H "

The following Table 2 gives details of further dyes of the formula##STR51## which can be produced by the process of this invention.

               Shade on Example         Polyester No. R.sub.20 R.sub.21     R.sub.22 R.sub.23 R.sub.24 R.sub.25 R.sub.26 R.sub.27 fibre       130 SO.sub.2 CH.sub.3 Br H Br H C.sub.2 H.sub.5 C.sub.2 H.sub.5 H red     violet  131 " Cl H Br NHCOCH.sub.3 " CH.sub.2 CH.sub.2 COOCH.sub.3 H     blue violet 132 " H H CH.sub.3 " " C.sub.2 H.sub.5 H red 133 " H H " H " C     H.sub.2 CH.sub.2 OCOCH.sub.3 H orange 134 " CH.sub.3 H H NHCOCH.sub.3 "     " H red orange 135 " H Cl H " " C.sub.2 H.sub.5 H " 136 " H H Cl     CH.sub.3 " CH.sub.2 CH.sub.2 OH H yellowish red 137 SO.sub.2 C.sub.6     H.sub.5 Cl Cl H NHCOCH.sub.3 " C.sub.2 H.sub.5 H red 138 Cl Cl Cl     SO.sub.2 CH.sub.3 H CH.sub.2 CH.sub.2 CN " H " 139 Cl Cl H " H C.sub.2     H.sub.5 C.sub.2 H.sub.5 H red violet 140 SO.sub.2 C.sub.6 H.sub.5 H H H     NHCOCH.sub.3 " " H orange 141 " H H H NHCOC.sub.2 H.sub.5 " " H " 142 H     H Cl SO.sub.2 CH.sub.3 H " " H " 143 H Cl H " H CH.sub.2 CH.sub.2 OH     CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H red orange 144 H Br H " H CH.sub.2     CH.sub.2 CN C.sub.2      H.sub.5 H " 145     ##STR52##      CH.sub.3 H H NHCOCH.sub.3 C.sub.2 H.sub.5 " H " 146 H H CH.sub.3     SO.sub.2 CH.sub.3 " CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2     OCOCH.sub.3 H red 147 H H " " H " " H red orange 148 H Cl " " H C.sub.2     H.sub.5 C.sub.2 H.sub.5 H " 149 Cl CH.sub.3 H " NHCOCH.sub.3 " " H red     violet 150      ##STR53##      " H CH.sub.3 " " " H red orange 151 SO.sub.2 CH.sub.3 " H " H " " H     orange 152 " OCH.sub.3 H Br NHCOCH.sub.3 " " H red 153 " " H OCH.sub.3 "     " " H " 154      ##STR54##      H H NO.sub.2 " " "  H violet 155 SO.sub.2 C.sub.2 H.sub.5 CH.sub.3 H "     " " " H " 156 SO.sub.2 C.sub.6 H.sub.5 " H SO.sub.2 CH.sub.3 " " " H red     157 H NO.sub.2 H " H " " H red 158      ##STR55##      " H H H CH.sub.2 CH.sub.2 CN CH.sub.2 CH.sub.2      OH H red 159     ##STR56##      " H Cl NHCOCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H violet 160     SO.sub.2 CH.sub.3 " H " " " CH.sub.2 CH.sub.2 COOCH.sub.3 H " 161 " " H     " H CH.sub.2 CH.sub.2 CN CH.sub.3 H red violet 162 " " Cl H NHCOCH.sub.3 C     .sub.2 H.sub. 5 C.sub.2 H.sub.5 H red 163 " " SO.sub.2 CH.sub.3 H " " "     H blue violet 164 " " H CF.sub.3 " " " H " 165      ##STR57##      CN H Br H " " H red orange 166      ##STR58##      CF.sub.3 H Cl NHCOCH.sub.3 CH.sub.2 CH.sub.2 OH CH.sub.2 CH.sub.2 OH H     red 167      ##STR59##      CN H H " C.sub.2 H.sub.5 C.sub.2 H.sub.5 H " 168 SO.sub.2 CH.sub.3     NO.sub.2 H CH.sub.3 NHCOCH.sub.3 " " H violet 169 " CN H NO.sub.2 " " "     H blue violet 170 " " H CN " CH.sub.2 CH.sub.2 OH CH.sub.2 CH.sub.2 OH     OCH.sub.3 blue 171 " " H " " CH.sub.2 CH.sub.2 COOCH.sub.3 CH.sub.2     CH.sub.2 COOCH.sub.3 " blue violet 172 SO.sub.2 C.sub.6 H.sub.5 " H " H     CH.sub.2 CH.sub.2 CN " H red 173 SO.sub.2 CH.sub.3 " H " CH.sub.3     CH.sub.2 CH.sub.2 OH C.sub.2 H.sub.5 H reddish blue 174 " " H " " "     CH.sub.2 CH.sub.2 OH H violet 175 SO.sub.2 C.sub.6 H.sub.5 " H " H     CH.sub.2 CH.sub.2 CN C.sub.2      H.sub.5 H red violet 176     ##STR60##      " H " CH.sub.3 " " H " 177 SO.sub.2 CH.sub.3 " H " NHCOCH.sub.3 H     CH.sub.2 CH.sub.2 OH CH.sub.3 " 178 " NHCOCH.sub.3 H Cl " C.sub.2     H.sub.5 C.sub.2 H.sub.5 H red 179 " CN Cl H H CH.sub.2 CH.sub.2 CH.sub.2     CH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 H violet 180 " " SO.sub.2     CH.sub.3 H NHCOCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H red violet 181 N     O.sub.2 SO.sub.2 C.sub.2 H.sub.5 H SO.sub.2 CH.sub.3 " " " H red 182     SO.sub.2 CH.sub.3 NHCOCH.sub.3 Cl H " " " H " 183 " NO.sub.2 H NO.sub.2     NHCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 O     CH.sub.3 blue 184 " " H " " " " OC.sub.2      H.sub.5 " 185 " " H " NHCOC.sub.2 H.sub.5 " " OCH.sub.3" 186 " " H " "     " " OC.sub.2 H.sub.5 " 187 " " H " NHCOCH.sub.3 CH.sub.2 CH.sub.2     OCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5 " " 188 " " H "     NHCHO CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3     OCH.sub.3 " 189 " " H " NHCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOC.sub.2     H.sub.5 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5 " " 190 SO.sub.2 CH.sub.3 "     H " NHCOCH.sub.3 CH.sub.2 CH.sub.2 CN CH.sub.2 CH.sub.2 OCOCH.sub.3     OC.sub.2 H.sub.5 " 191 " " H " NHCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2     OCOCH.sub.3 " H " 192 " " H " NHCOCH.sub.3 " " OC.sub.2 H.sub.5 " 193 "     " H " NHCOCH.sub.3 CH.sub.2 CH.sub. 2 COOCH.sub.3 CH.sub.2 CH.sub.2     COOCH.sub.3 OC.sub.2 H.sub.5 " 194 " " H " " CH.sub.2 CH.sub.2      OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 H " 195 " " H " " CH.sub.2     CH.sub.2 OCOOCH.sub.3 CH.sub.2 CH.sub.2 OCOOCH.sub.3 OC.sub.2 H.sub.5 "     196 " " H " " CH.sub.2 CH.sub.2 OCHO CH.sub.2 CH.sub.2 OCHO " " 197     SO.sub.2 C.sub.6 H.sub.5 " H " " CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2     CH.sub.2      OCOCH.sub.3 OCH.sub.3 " 198     ##STR61##      " H " " " CH.sub.2 CH.sub.2 OCOCH.sub.3 OC.sub.2 H.sub.5 " 199 SO.sub.2     C.sub.6      H.sub.5 " H " " " " " " 200     ##STR62##      " H " " " " OCH.sub.3 " 201 SO.sub.2 C.sub.6 H.sub.5 " H " " CH.sub.2     CH.sub.2 OCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5 " " 202      ##STR63##      " H " " " " OC.sub.2 H.sub.5 " 203 SO.sub.2 C.sub.6 H.sub.5 " H " NHCHO C     H.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub.3 " " 204      ##STR64##      " H " NHCOC.sub.2 H.sub.5 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5 CH.sub.2     CH.sub.2 OCOC.sub.2 H.sub.5 " " 205 SO.sub.2 C.sub.6 H.sub.5 " H " "     CH.sub.2 CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2 OCOCH.sub. 3 H " 206      ##STR65##      " H " NHCOCH.sub.3 " " " " 207 SO.sub.2 C.sub.6 H.sub.5 " H " "     CH.sub.2 CH.sub.2 CN " OC.sub.2 H.sub.5 " 208 " " H " " CH.sub.2     CH.sub.2 OCOCH.sub.3 CH.sub.2 CH.sub.2      OCOOCH.sub.3 " " 209     ##STR66##      " H " " CH.sub.2 CH.sub.2 OCHO CH.sub.2 CH.sub.2      OCHO " "

EXAMPLE 210

18 Parts of a 30% aqueous solution of sodium methanesulphinate are addedto a solution of 21.3 parts of[2-chloro-4-nitro-4'N-ethyl-N-β-trimethylammoniumethylamino-1,1'-azobenzene ]³⁰ C³¹ in 300 parts of dimethylformamide at 20°-25°.The temperature of the reaction solution is increased to 80°-90° and itis stirred for 6 hours. Subsequently it is cooled to 25° and run intoice-water. The dye is precipitated by the addition of common salt,filtered off and washed with concentrated common salt solution. The dyethus produced gives dyeings of rubine shade on polyacrylonitrile fibreswhich have excellent fastness properties.

The basic dyes detailed in the following Table 3 are of the formula##STR67## and can be produced in comformity with the foregoing Example.

    __________________________________________________________________________                                                             Shade on             Example                                                  Polyester            No   R.sub.20     R.sub.21                                                                              R.sub.22                                                                            R.sub.23                                                                          R.sub.24                                                                              R.sub.25                                                                           K       fibre                __________________________________________________________________________    211  SO.sub.2 CH.sub.3                                                                          SO.sub.2 CH.sub.3                                                                     H     H   H       C.sub.2 H.sub.5                                                                     ##STR68##                                                                            scarlet              212  "            SO.sub.2 N(CH.sub.3).sub.2                                                            Cl    H   H       "    N(CH.sub.3).sub.3                                                                     "                    213                                                                                 ##STR69##   NO.sub.2                                                                              H     NO.sub.2                                                                          CH.sub.3                                                                              C.sub.2 H.sub.5                                                                    "       blue violet          214  SO.sub.2 CH.sub.3                                                                          "       H     "   "       "                                                                                   ##STR70##                                                                            "                    215  "            Cl      H     "   H       CH.sub.3                                                                            ##STR71##                                                                            red violet           216  "            H       Cl    H   H       C.sub.2 H.sub.5                                                                     ##STR72##                                                                            orange               217  "            H       SO.sub.2 CH.sub.3                                                                   H   H       "                                                                                   ##STR73##                                                                            "                    218  "            NO.sub.2                                                                              H     NO.sub.2                                                                          NHCOC.sub.6 H.sub.5                                                                   "    N(CH.sub.3).sub.3                                                                     blue                 219  "            "       H     H   H       "    N(C.sub.2 H.sub.5).sub.3                                                              rubine               220                                                                                 ##STR74##   H       H     NO.sub.2                                                                          H       CH.sub.3                                                                            ##STR75##                                                                            bluish red           221  SO.sub.2 C.sub.2 H.sub.5                                                                   NO.sub.2                                                                              H     H   CH.sub.3                                                                              C.sub.2 H.sub.5                                                                     ##STR76##                                                                            bordeaux             __________________________________________________________________________

Representative dyestuffs of the foregoing Examples are as follows:

EXAMPLE 1 ##STR77## EXAMPLE 13 ##STR78## EXAMPLE 67 ##STR79## EXAMPLE 80##STR80## EXAMPLE 85 ##STR81## EXAMPLE 86 ##STR82##

Having thus disclosed the invention what we claim is:
 1. A compound ofthe formulawherein R₁₁ is phenyl or substituted phenyl, wherein eachsubstituent of substituted phenyl is independently fluoro, chloro,bromo, iodo, hydroxy, methyl, amino, methylamino, nitro or acetamido,R₁₂ is hydrogen, lower alkyl, formamido, lower alkylcarbonylamino,substituted lower alkylcarbonylamino, methoxycarbonylamino,ethoxycarbonylamino, benzamido, methylsulfonylamino orethylsulfonylamino, wherein the substituent of substituted loweralkylcarbonylamino is chloro, bromo, acetoxy, methoxy, ethoxy orphenoxy, R₁₃ is hydrogen, lower alkyl or lower alkoxy, R₁₄ is hydrogen,lower alkyl or substituted lower alkyl wherein the substituent is cyano,hydroxy, methoxy, ethoxy, cyanoethoxy, formyloxy, acetoxy, propionyloxy,methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,acetoxyethoxy or phenyl, and R₁₅ is hydrogen, lower alkyl or substitutedlower alkyl wherein the substituent is hydroxy, methoxy, ethoxy,cyanoethoxy, phenoxy, phenyl, methylamino, ethylamino, formyloxy,acetoxy, propionyloxy, benzoyloxy, methoxycarbonyl, ethoxycarbonyl,phenoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,phenoxycarbonyloxy, methoxyethoxycarbonyl, 1,1-dimethylhydrazinium A⁻,trimethylammonium A⁻, or triethylammonium A⁻, wherein A⁻ is an anion. 2.A compound according to claim 1wherein R₁₂ is hydrogen, lower alkyl,formamido, lower alkylcarbonylamino, substituted loweralkylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino,methylsulfonylamino or ethylsulfonylamino, wherein the substituent ofsubstituted lower alkylcarbonylamino is methoxy or ethoxy, R₁₃ ishydrogen or lower alkoxy, R₁₄ is lower alkyl or substituted lower alkylwherein the substituent is cyano, methoxy, formyloxy, acetoxy,propionyloxy or methoxycarbonyl, and R₁₅ is hydrogen, lower alkyl orsubstituted lower alkyl wherein the substituent is hydroxy, methoxy,cyanoethoxy, phenoxy, phenyl, formyloxy, acetoxy, propionyloxy ormethoxycarbonyl.
 3. A compound according to claim 2wherein R₁₁ isphenyl, 4-bromophenyl, 4-fluorophenyl, 4-iodophenyl, 2-methylphenyl,4-methylphenyl, 3-nitrophenyl, 4-acetamido-3-chlorophenyl,3-amino-6-chlorophenyl, 4-chloro-3-methylphenyl,4-chloro-3-methylaminophenyl, 2-chloro-4-nitrophenyl,4-chloro-3-nitrophenyl, 3,4-dichlorophenyl, 2-hydroxy-5-nitrophenyl or2-methyl-5-nitrophenyl, R₁₂ is hydrogen, methyl, ethyl, formamido,acetamido, propionamido, methoxyacetamido, methoxypropionamido,ethoxypropionamido, methoxycarbonylamino, ethoxycarbonylamino,methylsulfonylamino or ethylsulfonylamino, R₁₃ is hydrogen, methoxy orethoxy, R₁₄ is ethyl, butyl or β-substituted ethyl wherein thesubstituent is cyano, methoxy, formyloxy, acetoxy, propionyloxy ormethoxycarbonyl, and R₁₅ is hydrogen, ethyl, propyl, benzyl orβ-substituted ethyl wherein the substituent is hydroxy, methoxy,2-cyanoethoxy, phenoxy, phenyl, formyloxy, acetoxy, propionyloxy ormethoxycarbonyl.
 4. A compound according to claim 1 having the formula##STR83## wherein R³ is phenyl or phenyl substituted by methyl, fluoro,chloro, bromo, iodo, nitro or acetamido,R⁴ is lower alkyl, lower alkylsubstituted by chloro, bromo, methoxy, ethoxy or acetoxy or phenyl, withthe proviso that R⁴ is methyl or ethyl when X is --COO-- or --SO₂ --, R⁵is hydrogen, lower alkyl or lower alkoxy, R⁶ is lower alkyl or lowerakyl substituted by hydroxy, cyano, methoxy, ethoxy, cyanoethoxy,phenyl, methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy,ethoxycarbonyloxy, acetoxy or propionyloxy, R⁷ is hydrogen, lower alkylor lower alkyl substituted by hydroxy, methoxy, ethoxy, cyanoethoxy,phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, methoxyethoxycarbonyl,phenoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,phenoxycarbonyloxy, acetoxy, propionyloxy or benzoyloxy, and X is--CO--, --COO-- or --SO₂ --.
 5. A compound according to claim 4 havingthe formula ##STR84## wherein R³ is phenyl or tolyl,Y is lower alkanoyl,methoxycarbonyl or ethoxycarbonyl, R⁵ is hydrogen, methyl, methoxy orethoxy, R⁶ is lower alkyl or lower alkyl substituted by hydroxy,methoxy, ethoxy, acetoxy, propionyloxy, cyano or phenyl, and R⁷ ishydrogen, lower alkyl or lower alkyl substituted by hydroxy, acetoxy,propionyloxy, methoxy or ethoxy.
 6. The compound according to claim 5having the formula ##STR85##
 7. The compound according to claim 5 havingthe formula ##STR86##
 8. The compound according to claim 5 having theformula ##STR87##
 9. The compound according to claim 5 having theformula ##STR88##
 10. A compound of the formula ##STR89## wherein R₁₁ islower alkyl, substituted lower alkyl, phenyl or substituted phenyl,wherein the substituent of substituted lower alkyl is chloro or bromoand each substituent of substituted phenyl is independently fluoro,chloro, bromo, iodo, hydroxy, methyl, amino, methylamino, nitro oracetamido,R₁₂ is hydrogen, lower alkyl, formamido, substituted loweralkylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino,benzamido, methylsulfonylamino or ethylsulfonylamino, wherein thesubstituent of substituted lower alkylcarbonylamino is chloro, bromo,acetoxy, methoxy, ethoxy or phenoxy, R₁₃ is hydrogen, lower alkyl orlower alkoxy, R₁₄ is hydrogen, lower alkyl or substituted lower alkylwherein the substituent is cyano, hydroxy, methoxy, ethoxy, cyanoethoxy,formyloxy, acetoxy, propionyloxy, methoxycarbonyl, ethoxycarbonyl,methoxycarbonyloxy, ethoxycarbonyloxy, acetoxyethoxy or phenyl, and R₁₅is hydrogen, lower akyl or substituted lower alkyl wherein thesubstituent is hydroxy, methoxy, ethoxy, cyanoethoxy, phenoxy, phenyl,methylamino, ethylamino, formyloxy, acetoxy, propionyloxy, benzoyloxy,methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, methoxycarbonyloxy,ethoxycarbonyloxy, phenoxycarbonyloxy, methoxyethoxycarbonyl,1,1-dimethylhydrazinium A⁻, trimethylammonium A⁻, or triethylammoniumA⁻, wherein A⁻ is an anion.
 11. A compound according to claim 10whereinR₁₁ is lower alkyl, phenyl or substituted phenyl, wherein eachsubstituent of substituted phenyl is independently fluoro, chloro,hydroxy, methyl, amino, methylamino or nitro, R₁₃ is hydrogen or loweralkoxy, R₁₄ is lower alkyl or substituted lower alkyl wherein thesubstituent is cyano, acetoxy, methoxycarbonyl or methoxycarbonyloxy,and R₁₅ is hydrogen, lower alkyl or substituted lower alkyl wherein thesubstituent is hydroxy, phenoxy, acetoxy, benzoyloxy, methoxycarbonyl,phenoxycarbonyl, methoxycarbonyloxy, phenoxycarbonyloxy ormethoxyethoxycarbonyl.
 12. A compound according to claim 11wherein R₁₁is methyl, phenyl, 4-fluorophenyl, 4-methylphenyl, 3-nitrophenyl,3-amino-6-chlorophenyl, 4-chloro-3-methylaminophenyl,2-chloro-4-nitrophenyl, 3,4-dichlorophenyl, 2-hydroxy-5-nitrophenyl or2-methyl-5-nitrophenyl, R₁₂ is hydrogen, methyl, ethyl, formamido,methoxyacetamido, ethoxyacetamido, phenoxyacetamido, acetoxyacetamido,methoxypropionamido, ethoxypropionamido, methoxycarbonylamino,ethoxycarbonylamino, benzamido, methylsulfonylamino orethylsulfonylamino, R₁₃ is hydrogen, methoxy or ethoxy, R₁₄ is ethyl,butyl or β-substituted ethyl wherein the substituent is cyano, acetoxy,methoxycarbonyl or methoxycarbonyloxy, and R₁₅ is hydrogen, ethyl orβ-substituted ethyl wherein the substituent is hydroxy, phenoxy,acetoxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl,methoxycarbonyloxy, phenoxycarbonyloxy or methoxyethoxycarbonyl.
 13. Acompound of the formula ##STR90## wherein R₁₁ is lower alkyl,substituted lower alkyl, phenyl or substituted phenyl, wherein thesubstituent of substituted lower alkyl is chloro or bromo and eachsubstituent of substituted phenyl is independently fluoro, chloro,bromo, iodo, hydroxy, methyl, amino, methylamino, nitro or acetamido,R₁₂is hydrogen, lower alkyl, formamido, lower alkylcarbonylamino,substituted lower alkylcarbonylamino, methoxycarbonylamino,ethoxycarbonylamino, benzamido, methylsulfonylamino orethylsulfonylamino, wherein the substituent of substituted loweralkylcarbonylamino is chloro, bromo, acetoxy, methoxy, ethoxy orphenoxy, R₁₃ is lower alkyl or lower alkoxy, R₁₄ is hydrogen, loweralkyl or substituted lower alkyl wherein the substituent is cyano,hydroxy, methoxy, ethoxy, cyanoethoxy, formyloxy, acetoxy, propionyloxy,methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,acetoxyethoxy or phenyl, and R₁₅ is hydrogen, lower alkyl or substitutedlower alkyl wherein the substituent is hydroxy, methoxy, ethoxy,cyanoethoxy, phenoxy, phenyl, methylamino, ethylamino, formyloxy,acetoxy, propionyloxy, benzoyloxy, methoxycarbonyl, ethoxycarbonyl,phenoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,phenoxycarbonyloxy, methoxyethoxycarbonyl, 1,1-dimethylhydrazinium A⁻,trimethylammonium A⁻, or triethylammonium A⁻, wherein A⁻ is an anion.14. A compound of the formula ##STR91## wherein R₁₁ is lower alkyl,substituted lower alkyl, phenyl or substituted phenyl, wherein thesubstituent of substituted lower alkyl is chloro or bromo and eachsubstituent of substituted phenyl is independently fluoro, chloro,bromo, iodo, hydroxy, methyl, amino, methylamino, nitro or acetamido,R₁₂is hydrogen, lower alkyl, formamido, lower alkylcarbonylamino,substituted lower alkylcarbonylamino, methoxycarbonylamino,ethoxycarbonylamino, benzamido, methylsulfonylamino orethylsulfonylamino, wherein the substituent of substituted loweralkylcarbonylamino is chloro, bromo, acetoxy, methoxy, ethoxy orphenoxy, R₁₃ is hydrogen, lower alkyl or lower alkoxy, R₁₄ is hydrogenor substituted lower alkyl wherein the substituent is cyano, hydroxy,methoxy, ethoxy, cyanoethoxy, formyloxy, acetoxy, propionyloxy,methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,acetoxyethoxy or phenyl, and R₁₅ is hydrogen, lower alkyl or substitutedlower alkyl wherein the substituent is hydroxy, methoxy, ethoxy,cyanoethoxy, phenoxy, phenyl, methylamino, ethylamino, formyloxy,acetoxy, propionyloxy, benzoyloxy, methoxycarbonyl, ethoxycarbonyl,phenoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,phenoxycarbonyloxy, methoxyethoxycarbonyl, 1,1-dimethylhydrazinium A⁻,trimethylammonium A⁻, or triethylammonium A⁻, wherein A⁻ is an anion.15. A compound according to claim 14wherein R₁₁ is lower alkyl, phenylor substituted phenyl, wherein each substituent of substituted phenyl isindependently chloro, bromo, iodo, methyl, nitro or acetamido, R₁₂ ishydrogen, lower alkyl, formamido, lower alkylcarbonylamino, substitutedlower alkylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino,benzamido or methylsulfonylamino, wherein the substituent of substitutedlower alkylcarbonylamino is acetoxy or ethoxy, R₁₃ is hydrogen, loweralkyl or lower alkoxy, and R₁₅ is hydrogen, lower alkyl or substitutedlower alkyl wherein the substituent is hydroxy, methoxy, phenyl,formyloxy, acetoxy, propionyloxy, methoxycarbonyl, ethoxycarbonyl ormethoxycarbonyloxy.
 16. A compound according to claim 15wherein R₁₁ ismethyl, ethyl, phenyl, 4-bromophenyl, 4-iodophenyl, 2-methylphenyl,4-methylphenyl, 3-nitrophenyl, 4-acetamido-3-chlorophenyl,4-chloro-3-methylphenyl, 2-chloro-4-nitrophenyl, 4-chloro-3-nitrophenylor 3,4-dichlorophenyl, R₁₂ is hydrogen, methyl, formamido, acetamido,propionamido, ethoxyacetamido, acetoxyacetamido, methoxycarbonylamino,ethoxycarbonylamino, benzamido or methylsulfonylamino, R₁₃ is hydrogen,methyl, methoxy or ethoxy, R₁₄ is β-substituted ethyl wherein thesubstituent is cyano, methoxy, formyloxy, acetoxy, propionyloxy,methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy or 2-acetoxyethoxyor 3-acetoxypropyl, and R₁₅ is hydrogen, ethyl, propyl, benzyl,β-substituted ethyl wherein the substituent is hydroxy, methoxy, phenyl,formyloxy, acetoxy, propionyloxy, methoxycarbonyl, ethoxycarbonyl,methoxycarbonyloxy or ethoxycarbonyloxy or 3-acetoxypropyl.
 17. Acompound of the formula ##STR92## wherein R₁₁ is lower alkyl,substituted lower alkyl, phenyl or substituted phenyl, wherein thesubstituent of substituted lower alkyl is chloro or bromo and eachsubstituent of substituted phenyl is independently fluoro, chloro,bromo, iodo, hydroxy, methyl, amino, methylamino, nitro or acetamido,R₁₂is hydrogen, lower alkyl, formamido, lower alkylcarbonylamino,substituted lower alkylcarbonylamino, methoxycarbonylamino,ethoxycarbonylamino, benzamido, methylsulfonylamino orethylsulfonylamino, wherein the substituent of substituted loweralkylcarbonylamino is chloro, bromo, acetoxy, methoxy, ethoxy orphenoxy, R₁₃ is hydrogen, lower alkyl or lower alkoxy, R₁₄ is hydrogen,lower alkyl or substituted lower alkyl wherein the substituent is cyano,hydroxy, methoxy, ethoxy, cyanoethoxy, formyloxy, acetoxy, propionyloxy,methoxycarbonyl, ethoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,acetoxyethoxy or phenyl, and R₁₅ is hydrogen or substituted lower alkylwherein the substituent is hydroxy, methoxy, ethoxy, cyanoethoxy,phenoxy, phenyl, methylamino, ethylamino, formyloxy, acetoxy,propionyloxy, benzoyloxy, methoxycarbonyl, ethoxycarbonyl,phenoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,phenoxycarbonyloxy, methoxyethoxycarbonyl, 1,1-dimethylhydrazinium A⁻,trimethylammonium A⁻, or triethylammonium A⁻, wherein A⁻ is an anion.18. A compound according to claim 17wherein R₁₁ is lower alkyl, phenylor substituted phenyl, wherein each substituent of substituted phenyl isindependently chloro, bromo, iodo, methyl, nitro or acetamido, R₁₂ ishydrogen, lower alkyl, formamido, lower alkylcarbonylamino, substitutedlower alkylcarbonylamino, methoxycarbonylamino, ethoxycarbonylamino,benzamido or methylsulfonylamino, wherein the substituent of substitutedlower alkylcarbonylamino is acetoxy or ethoxy R₁₃ is hydrogen, loweralkyl or lower alkoxy, and R₁₄ is lower alkyl or substituted lower alkylwherein the substituent is cyano, methoxy, formyloxy, acetoxy,propionyloxy, methoxycarbonyl, ethoxycarbonyl or methoxycarbonyloxy. 19.A compound according to claim 18wherein R₁₁ is methyl, ethyl, phenyl,4-bromophenyl, 4-iodophenyl, 2-methylphenyl, 4-methylphenyl,3-nitrophenyl, 4-acetamido-3-chlorophenyl, 4-chloro-3-methylphenyl,2-chloro-4-nitrophenyl or 4-chloro-3-nitrophenyl, R₁₂ is hydrogen,methyl, ethyl, formamido, acetamido, propionamido, ethoxyacetamido,acetoxyacetamido, methoxycarbonylamino, ethoxycarbonylamino, benzamidoor methylsulfonylamino, R₁₃ is hydrogen, methyl, ethyl, methoxy orethoxy, R₁₄ is methyl, ethyl, butyl, β-substituted ethyl wherein thesubstituent is cyano, methoxy, formyloxy, acetoxy, propionyloxy,methoxycarbonyl, ethoxycarbonyl or methoxycarbonyloxy or3-acetoxypropyl, and R₁₅ is hydrogen, benzyl, β-substituted ethylwherein the substituent is hydroxy, methoxy, 2-cyanoethoxy, phenoxy,phenyl, formyloxy, acetoxy, propionyloxy, benzoyloxy, methoxycarbonyl,ethoxycarbonyl, phenoxycarbonyl, methoxycarbonyloxy, ethoxycarbonyloxy,phenoxycarbonyloxy or 2-methoxyethoxycarbonyl or 3-acetoxypropyl.
 20. Acompound of the formula ##STR93## wherein R₁₁ is methyl, ethyl,bromomethyl, phenyl, 4-bromophenyl, 4-fluorophenyl, 4-iodophenyl,2-methylphenyl, 4-methylphenyl, 3-nitrophenyl,4-acetamido-3-chlorophenyl, 3-amino-6-chlorophenyl,4-chloro-3-methylphenyl, 4-chloro-3-methylaminophenyl,2-chloro-4-nitrophenyl, 4-chloro-3-nitrophenyl, 3,4-dichlorophenyl,2-hydroxy-5-nitrophenyl or 2-methyl-5-nitrophenyl,R₁₂ is hydrogen,methyl, ethyl, formamido, acetamido, propionamido, methoxyacetamido,ethoxyacetamido, phenoxyacetamido, acetoxyacetamido,methoxypropionamido, ethoxypropionamido, methoxycarbonylamino,ethoxycarbonylamino, benzamido, methylsulfonylamino orethylsulfonylamino, R₁₃ is hydrogen, methyl, ethyl, methoxy or ethoxy,R₁₄ is methyl, ethyl, butyl, β-substituted ethyl wherein the substituentis cyano, methoxy, formyloxy, acetoxy, propionyloxy, methoxycarbonyl,ethoxycarbonyl, methoxycarbonyloxy or 2-acetoxyethoxy or3-acetoxypropyl, and R₁₅ is hydrogen, methyl, ethyl, propyl, benzyl,β-substituted ethyl wherein the substituent is hydroxy, methoxy,2-cyanoethoxy, phenoxy, phenyl, formyloxy, acetoxy, propionyloxy,benzoyloxy, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl,methoxycarbonyloxy, ethoxycarbonyloxy, phenoxycarbonyloxy or2-methoxyethoxycarbonyl or 3-acetoxypropyl,with the proviso that whenR₁₁ is methyl, R₁₂ is acetamido and R₁₃ is hydrogen, at least one of R₁₄and R₁₅ is other than ethyl.
 21. The compound according to claim 20having the formula ##STR94##
 22. The compound according to claim 20having the formula ##STR95##
 23. The compound according to claim 20having the formula ##STR96##
 24. The compound according to claim 20having the formula ##STR97##
 25. The compound according to claim 20having the formula ##STR98##
 26. The compound according to claim 20having the formula ##STR99##